Substituted amino-s-triazines

ABSTRACT

Triazine compounds are disclosed which are derivatives of symmetrical triazine having two radicals of the structure THERE BEING AT LEAST ONE METAL COORDINATING GROUP OF THE STRUCTURE -CHR4COOM, wherein M, Z, R2, R3 and R4 are as defined hereinafter. These compounds are useful for coordinating with and removing metals from solutions or for preparing resins capable of removing metals from solutions.

United States Patent DAlelio 51 June 13, 1972 [5 SUBSTITUTED AMINO-S-TRIAZINES Primary Ford Attorney-Walter J. Monacelli [72] Inventor: Gaetano F. DAlelio, South Bend, Ind.

[73] Assignee: Walter J. Monacelli, Cleveland, Ohio a ABSTRACT pan mterest Triazine compounds are disclosed which are derivatives of [22] Filed: Jan. 2, 1970 symmetrical triazine having two radicals of the structure [21] Appl. No: 5,399

R1 2 R1 R2 R1 32 Related US. Application Data I I I I I I -NN, -N-CHR(CHR4)D'N, or -NZN, [62] Division ofSer. No. 638,654, May 15, 1967.

[52] US. Cl 260/2496, 260/2498, 260/2499,

260/2495, 260/242 there being at least one metal coordinating group of the struc- [51] Int. Cl. ..C07d 55/20 ture CHR4COQM wherein M, 2 2 R3 and 4 are as 58 Field ofSearch ..260/249.6, 249.8, 249.9, 242 defined hereinaften These Compounds are useful for coop dinating with and removing metals from solutions or for [56] References cued preparing resins capable of removing metals from solutions.

UNITED STATES PATENTS 2,328,961 9/1943 D'Alelio et a1 ..260/249.8 X 3,216,975 1 l/1965 Kunde et a1 ..260/249.8 X 7 Claims, N0 Drawings 3,310,557 3/1967 Kleemann ..260/249.8 X

SUBSTITUTED AMINO-S-T'RIAZINES This application is a divisional application of copending application Ser. No. 638,654 filed May 15, 1967.

This invention relates to new chemical compounds and more particularly to triazine derivatives. The invention is concerned especially with the production and use of new and useful triazines having the property of coordinating metal ions.

The chemical compounds of this invention may be represented by the general formula,

wherein Y represents any monovalent radical and T represents a coordination group more fully described hereinafter, and n represents an integer of l to 3. When n is 3, 3-n is zero; when n is 2, FM: is l; and when n is l, n-l is 2. More specifically, this invention is concerned with a triazine derivative having the formula,

, wherein at least one of said valencies is attached to a T group.

In the above triazine formula, Y can be R which represents hydrogen or any monovalent hydrocarbon radical, whether saturated or unsaturated, substituted or unsubstituted, aliphatic, carbocyclic, aryl or heterocyclic, monoor polynuclear etc. Examples of suitable hydrocarbon groups represented by R are aliphatic, aromatic, e.g., methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, butenyl, amyl, hexyl, allyl, methallyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, diphenyl, naphthyl, tolyl, xyxlyl, ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl, benzyl, phenylallyl, phenylpropyl, etc., and their homologues, as well as those groups with one or more of their hydrogen atoms substituted by halogens, as, for example, fluorine, chlorine, nitro groups, nitroso groups, amino groups, carboxy groups, etc.; Y can also be hydroxyl and the alkoxy and aryloxy radicals of aliphatic, cycloaliphatic, aromatic and heterocyclic hydroxy compounds, such as methyl alcohol, ethyl alcohol, butyl alcohol, isobutyl alcohol, dodceyl alcohol, phenol, the o-, m, and pcresols, the xylenols, the naphthols, ethylene glycol, methyl glycol ether, butyl glycol ether, glycerine, pentaerythritol, naphthol, hydroxy pyridine, including the alkoxy and aryloxy radicals of hydroxy acids and esters, such as lactic acid, ethyl lactate, allyl lactate, methyl salicylate, and the chloro derivatives such as chlorophenol, chloronaphthol, ethylene chlorohydrin, and the acetoxy derivatives such as acetoxyethyl alcohol, etc., and these radicals are represented by RO; Y can also be R-S groups which are the mercapto equivalents to RO; Y can also be NR that is, an amino group, a monsubstituted amino group or a disubatituted amino group, as for example, the radicals of methyl amine, ethyl amine, butyl amine, nonyl amine, benzyl amine, dimethyl amine, aniline, naphthylamine, ehtanolamine, diethanolamine, diisopropylamine, methylaniline, piperidine, amino-pyridine, and the hydrazine radicals, namely, R NNR- from hydrazine, unsymmetrical dimethylhydrazine, symmetrical dimethylhydrazine, trimethylhydrazine, phenylhydrazine; Y can also be the N-radicals of the aminoacids, the aminoesters, the aminoamides, and the aminonitriles, some specific examples of which are Y can also be radicals of alkylene imines, such as, for example,

and the radicals of malonic esters and substituted malonic esters, nitriles, and amides, such as, for example, CH(COOCH3)zm' CH(COOCH CH-CH2)z, CH(CN) etc., or Y can be the radical of another triazinyl ring, e.g., (CN NH) (C N;,), (HO) (C;,N or the triazine ring can be attached through a bridge, such as [(CH N] (C N NHCl-hCl-QNH- (C H NH) (C;,N )OCH CH O, (H N (CH )NHCH CH O etc.; Y can also be chlorine, bromine, CN, COOR, etc.; as well as T.

The Y group can also be a solubilin'ng group, or a group modified to impart solubility of the triazine compound in water or in organic solvents. A few illustrative examples of water solubilizing groups are H(OCH CH ),,,O,

etc., wherein n has a numerical value of at least 1 and can beashighas 15 to 20.

When the new compounds of this invention contain Y groups of the type illustrated above, the compounds are nonresinous and non-polymeric and function as ligands in the formation of coordination compounds useful in the preparation of pigments and for removing metal ions from solutions. Because of the trivalent nature of the symmetrical triazine ring, a large number of permissible Y groups can be attached to the ring, including chemically active groups. When the Y groups are such that they can undergo addition or condensation polymerizations, then resins and polymers are readily prepared which are characterized by having within their repeating units a triazine ring to which at least one T group is attached. Furthermore, it is not necessary to prepare polymers of this type by polymerization reactions involving one or two Y groups, since it is possible, as shown hereinafter, to react many of the non-polymeric compounds of this invention with preformed polymers thereby attaching the tn'azinyl coordination moiety to the preformed polymer.

Thus, the Y group can also be a postreactive group, such as an aldehyde reactive group, which may be designated as an A group, by which the new compounds of this invention can be converted to condensation products by reaction with the aldehydes. polymeric aldehydes, aldehyde-addition products,

etc.,such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, acrolein, aldol, glucose, dimethylol urea, trimethylol melamine, hexarnethylol melamine, etc.

The aldehydereactable group, A, is a grouping of atoms or radicals that react with aldehyde or polymeric-aldehydes to form a derivative such as illustrated by the following:

As illustrative examples of the aldehyde-reactable group, A, there are mentioned the following groups:

OH OH as disclosed in my U.S. Pat. No. 2,295,562, issued Sept. 15, 1942, wherein x is an integer of at least 1 and not more than 2, Y represents a member of the class consisting of oxygen and sulfur, and R represents a member of the glass consisting of hydrogen and monovalent hydrocarbon and halohydrocarbon radicals;

i N R-N RC-NH R.

as disclosed in my U.S. Pat. No. 2,295,565, issued Sept. 15, 1942, wherein Y represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halohydrocarbon radicals;

as disclosed in my U.S. Pat. No. 2,295,562, issued Sept. 15, 1942, wherein R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halohydrocarbon radicals;

as disclosed in my U.S. Pat. No. 2,312,688, issued Mar. 2, 1943, wherein Y represents a member of the class consisting of oxygen and sulfur and R represents a member of the class consisting of hydrogen and hydrocarbon radicals and halohydracarbon radicals;

wherein Z represents an aryl nucleus and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon radicals and substituted hydrocarbon radicals:

as disclosed in my U.S. Pat. No. 2,312,700, issued Mar. 2, 1943, wherein n represents an integer and is at least one and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, Y represents a divalent carbocyclic radical and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon radicals and substituted hydrocarbon radicals; NHR, as disclosed in my U.S. Pat. No. 2,335,846, issued Dec. 7, 1943 wherein R represents a member of the class consisting of hydrogen and monovalent radicals and halohydrocarbon radicals; -ZCONHR, wherein Z represents a divalent hydrocarbon radical and R represents hydrogen and a monovalent hydrocarbon radical and substituted hydrocarbon radicals; BZCONHR, wherein B represents a member of the class consisting of oxygen, sulfur and NR, Z represents a divalent hydrocarbon radical and substituted hydrocarbon radicals, and R represents a member of the class of hydrogen and monovalent hydrocarbon radicals and substituted hydrocarbon radicals; HNRNR, wherein R represents a member of the class consisting of hydrogen and monovalent hydrocarbon radicals and substituted hydrocarbon radicals; l-lO-Z, wherein Z represents a divalent aromatic radical and substituted hydrocarbon radicals as hereinabove defined. A few typical triazine compounds are 1 C034) (CzNQli P (0 RM 2 and etcs, HOZ-NR, wherein R represents hydrogen and monovalent hydrocarbon radicals and substituted hydrocarbon radicals, and Z represents a divalent aromatic radical and substituted hydrocarbon radicals as hereinabove described. A few typical examples are 3 (HQCsH4NH)7(CsNa)- I (0 R):

and

etc. RCONHNR, where R represents hydrogen and a monovalent hydrocarbon radical and substituted hydrocarbon radicals as previously defined hereinabove; R NCYNR CHR', as disclosed in my U.S. Pat. No. 2,339,623, issued Jan. 18, 1944, wherein Y represents oxygen or sulfur, at least one R represents hydrogen and the other Rs represent hydrogen, a monovalent hydrocarbon radical or a monovalent halogenated hydrocarbon radical, and R represents hydrogen or a monovalent aliphatic, carbocyclic or aromatic hydrocar bon radical of not more than six carbon atoms, etc.;

may be demonstrated by comparing non-polymeric molecules containing such bonds. The bond in the former is ionic and similar to those that exist in such compounds as sodium phosphate, copper acetate, nickel sulfate, aluminum nitrate and many other salts. The bonds in the latter metals such as chromium, iron, cobalt, molybdenum, uranium, nickel, copper, zinc platinum, mercury, gold, silver, titanium, zirconium, vanadium, etc. A typical example of such a coordination compound is hexamine-cobalt( Ill) chloride, whose formula is [CO(NH )]CI this compound is prepared by reacting cobaltic chloride, CoCl which has its ionic valencies satisfied, with 6 moles of ammonia whereby the ammonia molecules are coordinated to the cobalt atom through non-ionic covalent linkages. Ethylene diamine will also complex with cobaltic chloride to give trisethylenediamine-cobalt(lIl) chloride,

HzN CH; M t 1 HzN CH1 3 When the complexing compound, such as ethylenediamine, can occupy simultaneously more than a single coordinating position, ring formation can occur and ring structures may be found in the complex. Such ring compounds are known as chelate compounds. The ring-forming groups are known as polydentate groups or as chelating groups, in contrast to the monodentate groups which may coordinate without forming ring or chelate compounds.

A large number of organic compounds containing suitable substituent groups function as chelating compounds of which ethylenediamine, diethylene triamine, etc., are typical examples. Another example is 2,2'-dipyridyl which complexes with ferrous chloride to give Other organic compounds which contain in their structure both salt forming groups and neutral donor groups can, through coordination or chelation, satisfy both the oxidation number of, and the coordination number of many metal ions, a typical example of which is the copper (ll) chelate of 8- hydroxy- O at N N Glycine and substituted glycines behave similarly as shown in copper (II) glycinate,

Accordingly, it is a proposal of this invention to attach T groups which act as coordination groups to the triazine rings, in which the T groups are selected from the class consisting of illustrative examples of the group are:

-NH-NHC H 0 OM;

an integer of one to six. A few typical examples of these groups are:

wherein R, R and B have the same meaning as described hereinabove, and Z is a divalent aromatic hydrocarbon radical containing six to twelve carbon atoms. A few illustrative examples of these groups are:

NH CeHKCHahNHCH COOM; NHCmHqNHCHzCOOM; etc.

O CHRKCHR) N wherein R R R and n have the same meaning as defined hereinabove, and a few illustrative examples are:

wherein Z, R and R have the same meaning as defined hereinabove, a few illustrative examples of which are:

0C.HtN CCO0M; 0-C,H (CH;)N(CH=C00M)1, etc.

In general, the triazine compounds used in the practice of this invention can be prepared conveniently by reacting in the presence of a hydrohalide acceptor, HAC, the corresponding halotriazines, for example, the bromoor chloro-trian'nes with the corresponding halotriazines, for example the bromoor chloro-triazines with the corresponding TH compounds wherein T is as previously defined, and H is an active hydrogen attached to the T group, e.g., (C N )Cl 3 TH "25' )Cl TH i (Y). ,(C N )T, and some specific examples of the above reactions are (NHNHCH COONa Alternately, these compounds can be prepared by using a halotriazine containing a T group as a substituent and reacting it with a compound containing a reactive hydrogen represented by YM, as for example:

The present invention is based on the discovery that new and valuable materials are obtained by having at least one T group of the type described above attached to the traizine ring. They can be used in the treatment of water to coordinate metallic ions and to maintain the ions in solutions when watersolubilizing groups are attached to the triazine ring, e.g., AS such they are useful in laundering, chemical processing, etc. They can also be used in the preparation of stable pigments as for example the copper coordinate of (C N )(NHNCH COOH) is a stable blue and the cobalt coordinate is a stable red. These coordinate-pigments are water insoluble, especially if to the triazine there is attached one or two Y groups contributing to water insolubility, e.g., (C,,H,,) N(C;,N;,)NHN(CH COOM) and ](C H N] C N NHN(CH COOM and they become organophilic when Y contains hydrocarbon groups such as (c ll Nl-i) C N ,(NHCH CH NCH COOM) and C, H ,,NH C N [OCH CH N(CH COM) The compounds of this invention having suitable Y groups can be used also to prepare addition and condensation polymers which coordinate with metal ions. One class of condensation polymers can be prepared when the Y group attached to the triazine ring is an aldehyde reactable group as previously described herein, such as in NH (C N )NHNKIH COOM) by reaction with an aldehyde, including aldehydes, hydroxy aldehydes and aldehyde addition products, e.g., paraformaldehyde, aldol, glucose, dimethyl urea, the methylol melamines, etc, to prepare products having utility as chelating resins for the isolation and separation of metal ions from dilute or concentrated solutions, as well as utility in the plastics, coating and impregnating arts. As chelating resins they are particularly useful in recovering the metals of the common chelating forming metals, such as Al Ti, V, Si, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Y, Zr, Cb, Mo, Tc, Rn, Pl, Pd, Ag, Cd, In, Sn, Sb, Hf, Ta, W, Rh, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, the lanthanides, the actinides, Sc, Ca, and Mg, and for separating the metals from each other.

In preparing condensation products with aldehydes and the triazines of this invention, the initial condensation reaction can be carried out at normal or elevated temperatures, at atmospheric, sub-atmospheric, or super-atmospheric pressures, and under natural, alkaline, or acid conditions. Preferably, in most cases, the reaction between the components is initiated under alkaline conditions.

Any substance yielding an alkaline or an acid aqueous solution can be used in obtained alkaline or acid conditions for the initial condensation reaction. For example, an alkaline substance such as sodium, potassium carbonate, mono di-, or triamines, etc., can be used. in some cases, it is desirable to cause the initial condensation reaction between the com ponents to take place in the presence of a primary condensation catalyst and a secondary condensation catalyst. The primary catalyst can be either an aldehyde-non-reactable nitrogen-containing basic tertiary compound, e.g., tertiary amines such as trialkyi (e.g. trimethyl, triethyl, etc.) amines, or an aldehyde-reactable nitrogen-containing basic compound, for instance, ammonia, primary amines (e.g., ethylamine, propyl amine, etc.) and secondary amines (eg. dipropylarnine, dibutylamine, etc.). The secondary condensation catalyst, which ordinarily is used in an amount less than the amount of the primary catalyst, advantageously is a fixed alkali, for instance, a carbonate, cyanide, or hydroxide of an alkali metal (eg sodium, potassium, lithium, etc.

Illustrative examples of acid condensation catalysts that can be employed are inorganic or organic acids, such as hydrochloric, sulfuric, phosphoric, acetic, lactic, acrylic, malonic, etc., or acid salts, such as sodium acid sulfate, monosodium phosphate, monosodium phthalate, etc. Mixtures of acids, of acid salts, or acids and acid salts can be employed, if desired.

The reaction between the aldehyde, e.g., formaldehyde, and the triazine derivative can be carried out in the presence of solvents, diluents, fillers, or other natural or synthetic resinous bodies, or while admixed with other materials that also can react with the aldehyde compound or with the triazine derivative, e.g., ketones, urea, thiourea, selenourea, iminourea (guandidine), substituted ureas, thioureas, and iminoureas, numerous examples of which are given in my US. Pat. No. 2,322,566, issued June 22, 1943; monoamides of monocarboxylic acids and polycarboxylic acids and polyamides of polycarboxylic acid, e.g., acetamide, halogenated acetamides (e.g. chloroacetamide), maleic monoamide, malonic monoamide, phthalic monoamide, maleic diamide, fumaric diamide, malonic diamide, itaconic diamide, succinic diamide, phthalic diamide, the monoamide, diamide and triamide of tricarballylic acid, etc.; aldehyde-reactable diazine compounds, such as are disclosed in my US. Pat. No. 2,382,21 l, issued Aug. l4, 1945; amino-triazines, e.g., melamine, ammeline, ammelide, melem, melam, melon, etc., phenol and substituted phenols, eg, the cresols, the xylenols, the tertiary alkylphenols and other phenols such as mentioned in my US. Pat. No. 2,339,411; monohydric and polyhydric alcohols, e.g., butyl propylene glycol, pentaerythritol, polyvinyl alcohol, etc., amines including aromatic amines, e.g., aniline, etc., and the like. In such cases, the triazine derivative should represent 5-95 percent by weight of the aldehyde reactive portion of such mixture.

The modifying reactants can be incorporated with the triazine derivative and the aldehyde to form an intercondensation product by mixing all the reactants and effecting condensation therebetween or by various permutations of reactants. For instance, a partial condensation product can be formed of ingredients comprising (i) urea or melamine or urea and melamine, (2) a triazine derivative of this invention, (3) an a]- dehyde, including polymeric aldehydes, hydroxy aldehydes and aldehyde-addition products, for instance, formaldehyde, paraformaldehyde, dimethylol urea, a polymethylol melamine; and thereafter reaction effected between this partial condensation product, and, for example, a curing reactant, specifically a chlorinated acetamide or an amino acid.

Some of the condensation products of this invention are thermoplastic materials even at an advanced stage of condensation, while others are thermosetting or potentially thermosetting bodies that convert under heat or under heat and pressure to an insoluble infusible state. The thermoplastic condensation products are of particular value as plasticizers for other synthetic resins. The thermosetting, or potentially The liquid intermediate condensation products of this invention can be concentrated by the removal of, or diluted further by the addition of volatile solvents, to form liquid coating compositions of adjusted viscosity and concentration. The heat-convertible or potentially heat-convertible resinous condensation products can be used in the liquid state, for instance, as impregnants for wood, leather, paper and other porous bodies; as surface-coating materials in the production of paints, varnishes, lacquers, enamels, etc., for general adhesive applications in producing laminated articles, and for other purposes. The liquid, heat-hardenable or potentially heathardenable condensation products also can be used directly as casting resins, while those which are gell-like by nature in the partially condensed state can be granulated and dried to form clear, unfilled heat-convertible resinous products.

In producing these new condensation products the choice of the aldehyde is dependent largely on economic considerations and upon the particular properties desired in the finished product. Preferred aldehydic reactants are formaldehyde and compounds engendering formaldehyde, e.g., paraformaldehyde, hexamethylene, tetraamine, etc. Illustrative examples of other aldehydes that can be employed are acetaldehyde, propionaldehyde, butyraldehyde, heptaldehyde, octaldehyde, acrolein, methacrolein, crotonaldehyde, benzaldehyde, furfural, hydroxyladehydes (e.g., aldol, glucose, glycollic aldehyde, glycealdehyde, etc.), mixtures thereof or mixtures of formaldehyde (or compounds engendering formaldehyde) with such aldehydes. Illustrative examples of aldehyde-addition products that can be used instead of the aldehydes themselves are the mono-and poly-(N-carbinol) derivatives, particularly the monoand polymethylol derivatives of urea, thiourea, selenurea, and substituted ureas, thioureas, selenoureas, and iminoureas, monoand poly-(N-carbinol) derivatives of amides or polycarboxylic acids, e.g., maleic itaconic, fumaric, adipic, rnalonic, succinic, citric, phthalic, etc., monoand poly(N-carbinol) derivatives of the aminotriazoles, monoand poly-(N-carbinol) derivatives of the aminotriazines. Particularly good results are obtained with active methylene-containing bodies as a methylol urea, more particularly monoand dimethylol ureas, a methylol aminotriazine, more particularly a methylol melamine, e.g., monomethylol melamine and polymethylol melamines (di-, tri-, tetra-, penta-, and hexamethylol melamines). Mixtures of aldehydes and aldehyde-addition products can be employed, e.g., mixtures of formaldehyde and methylol compounds, such, for instance, as dimethylol urea, trimethylol melamine, hexamethylol melamine, etc.

The ratio of the aldehydic reactant to the triazine derivative can be varied over a wide range depending upon the particular properties desired in the finished product. Ordinarily these reactants are employed in an amount corresponding to at least 1 mole of the aldehyde, especially formaldehyde, for each mole of the triazine derivative. Thus, for example, 1 to 7 or 8 or more moles of an aldehyde can be used for each mole of the triazine derivative. When an aldehyde is available for reaction in the form of an alkylol derivative, more particularly a methylol derivative such, for instance, as dimethylol urea, trimethylol melamine, etc., then higher amounts of such aldehyde-addition products are used, for instance, from 2 to 3 up to to or more moles of such alkylol derivatives for each mole of the triazine derivative.

As indicated hereinabove, the properties of the fundamental resin can be varied widely by introducing other modifying bodies before, during, or after effecting condensation between the primary components. Thus modifying agents that can be used include, for example, methyl, ethyl propyl, isopropyl, isobutyl, hexyl, etc., alcohols; polyhydric alcohols, such as, for example, diethylene glycol, triethylene glycol, pentaerylthritol, etc., alcohol ethers, e.g., ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc.; amides, such as formamide, steararnide, acrylarnide, benzene sulfonamides, toluene sulfonamide, the aryl disulfonamides, adipic diamide, phthalamide, etc.; amines, e.g., ethylene diamine, phenylene diamine, etc.; ketones, including halogenated ketones, etc., nitriles, including halogenated nitriles, e.g., acrylonitrile, methacrylonitrile, succinonitrile, fumaryl nitrile, chloroacetonitriles, etc.; acylated ureas, more particularly halogenated acylated ureas of the kind described in my U.S. Pat. No. 2,851,559, and others.

The modifying bodies can also take the form of high molecular weight bodies with or without resinous characteristics, for example, hydrolyzed wood products, fonnalized cellulose derivatives, lignin, protein aldehyde condensation products, aminotriazine, aldehyde condensation products, aminotriazole-aldehyde condensation products, polyacrylamide, styrene-maleic imide copolymers, etc. Other examples of modifying bodies are the urea-aldehyde condensation products, the aniline-aldehyde condensation products, furfural condensation products, phenol-aldehyde condensation products, modified or unmodified, saturated or unsaturated polyhydric-alcohol-polycarboxylic acid condensation products, water-soluble cellulose derivitives, natural gums and resins, such as shellac, rosin, etc.; polyvinyl compounds, such as polyvinyl esters, e.g., polyvinyl acetate, polyvinyl butyrate, etc., polyvinyl ethers including polyvinyl acetals, especially polyvinyl formal, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers and various reinforcing fillers (e.g., wood flour, glass fibers, including difibrated asbestos, mineral wool, mica, cloth cuttings, glass cloth, glass mat, etc.) can be compounded with the resin in accordance with conventional practice to provide various thermoplastic and thermosetting molding compositions.

The modified and unmodified resinous compositions of this invention have a wide variety of uses. For example, in addition to their use in the production of molding compositions, they can be used as modifiers of other natural and synthetic polymers, as laminating varnishes in the production of laminated articles wherein sheet materials, e.g., paper, cloth, sheet asbestos, glass mats and glass fibers, etc., are coated and impregnated with the resin, superimposed and thereafter united under heat or heat and pressure. They can be used in the production of wire coatings or baking enamels from which insulated wires and other coated products are made; for bonding or cementing together mica flakes to form a laminated mica article, for bonding together abrasive grains in the production of resin-bonded abrasive articles such, for instance, as giindstones, sandpapers, emery cloths, etc., in the manufacture of electrical resistors, etc. They can also be employed for treating cotton, linen, and other cellulosic materials in sheet or other form. They can also be used as impregnants for electrical coils and for other electrically insulating applications.

One aspect of the present invention is based on the discovery that new and valuable materials having particular utility in the polymer, plastics, impregnating, and coating arts can be produced by effecting reaction between ingredients comprising an aldehyde, including polymeric aldehydes and aldehyde-addition products, and triazine compounds of the kind described hereinabove. The modified and unmodified condensation products have a wide variety of uses. Those condensation products having the T grouping can be used as molding compounds, laminating varnishes, impregnants alone or with other polymers and fillers, in the conventional manner; they act as preservatives for cellulosic substances, such as paper, wood, cotton, wool, leather, silk, proteins and the like; and they can also be used as resins to increase the wet-strength of paper and wood pulps. Those condensation products containing an H TSOJH or -A (03h grouping can be used as ion exchange resins, as preservatives, as their copper or 8-hydroxy quinoline salt, as additive-binders to insecticidal formulations, and as additives to increase the wet strength of paper while preserving it. The calcium, zinc,

and magnesium salts of these products can be used as molding compounds and as modifiers for other natural and synthetic polymers, for example, in laminating varnishes and in the production of laminated products wherein sheet materials, e.g., paper, cloth sheet asbestos, glass mats, glass fibers, etc., are coated and impregnated with resin, superimposed and thereafter united under heat and pressure.

The condensation products of this invention containing chromium are particularly useful in the treating and tanning of leathers. As is well known, resin tannage should be water-soluble or water-dispersible and their solutions should tolerate fair concentration of salt. They should be capable of penetrating into the skin before and during early stages of tanning and before and during the early stages of polymerization. Preferably the tannage should be very pale or water-white in color. These objectives are achieved by using products made according to the practice of this invention; for example, the tolerance to the salt solution, that is, the salting-out value of the water-solubility can be changed by varying the number of T acids attached to the triaane ring, e.g., (NH,)(C N or (NH,) (C N )T or by using a sulfonic acid substituent along with the T, e.g., (NH-zllCaNsX-NHCsHaSOgNflKT) OI (NHgCONHNH) (NHC H SO Na)(T) or by condensing with urea, melamine, dimethylol urea, dimethylol melamine. trimethylol melamine, phenol alcohols, etc., and by varying the ratio of such modifying condensing substances. Also by using the products made according to the practice of this invention, the fat-liquoring characteristics of the tannage can be readily changed by selecting appropriate R groups in the triazine derivative, for example by using (Cm 21 )2 3 3) and (C l-l Nl-lflC N KD instead of the corresponding NH substituted triazines. Furthermore, the solubility or dispersibility of the condensation product can be increased by using as Y groups those groups that increase solubility such as HOCHzCl'izM-O- and H(OCH-;CH- ),,O where n has a numerical value of one to 50 or more. Also, these condensation products can be modified so that they act as flame-retardants as well as preservatives not only for leather but for such substances as wool, cotton, wood, paper, etc., by using compounds in the practice of this invention in which Y represents groups such as:

The triazine derivatives embraced by the formulas of the various classes of compounds used in producing the new condensation products of this invention are the triazine derivatives having substituents indicated by the groups attached to the structure,

c-Nnmcmcoomii 1 u (C (CHrhC O0 CHzCHzNHC CNHCHeCHaO -dm Further, by the use of such alcohols, polyurethanes can also be prepared as another class of condensation polymers, such l l ocNcrnncnnNcoocnrcnmn- C-NHN (CHzCOONB):

The addition polymers are classified as a class distinct from condensation polymers. l have also discovered that I can prepare addition polymers falling within the scope of this invention.

One class of addition polymer is the linear polymer derived from a triazine derivative containing at least one T group, and one Y or A group containing a polymerizable terminal group as in the monomers: CHz=CHCOOCHzCHzNH(CzNz)IN(CH:):I[NHN(CH:COOM)2];

CHz=CHCrH4NH(C:Ni)[N(CH:)zliNHN(CH:COOM)2l;

CH, CH;& COOCHaCHzNH(C;Nz)lN(CH:):][NHN (CHzCOOMhl;

CHz==CHCiH1O (CiN:)[N(CH:)2I[NHN(CH:COOM)2L wherein polymerization of the CHr=C group in the monomer results in the polymer.

Another class of addition polymers is the crosslinked polymers derived from a triazine derivative containing one T group and 2 groups containing a group as in the monomers:

A further class of addition polymer of this invention is the addition polymerization products of a triazine derivative containing at least one T group and at least one other group containing an oxirane su'ucture, as in the wnrciicmoicmoimiibiinamcmcooun:

A still further class of addition polymers is derived by the polymerizau'on of a triazine derivative containing at least one '1 group and at least one alkylene imino group such as in the monomer:

N (CaNa) [NHN(CH2COON8)2].

Many of the triazine derivatives of this invention can also be used to modify preformed polymers and copolymers having reactive hydrogens, such as cellulose, polyvinyl alcohol, wool, para cresol-aldehyde resins, polyvinyl amine, polyacrylic acid, etc., as illustrated by polyvinyl alcohol thus:

( KE M O aNaHNHNHCHzCOONah.

wherein at least one of the valency is attached to a T group and at least one other valency is attached to a polymer.

Thus it may be seen that the Y groups may be any polymerizable group as well as a non-polymerizable group, and that thus the Y group itself may be a polymer or preformed polymer, and that the compounds of this invention can be classified as symmetrical triazines having the structure,

to which is attached at least one and no more than three T groups, in which the T groups are as defined hereinabove.

These coordination resins difier from the conventional ionexchange resins. The conventional ion-exchange resins are polymer matrices to which are attached functional acidic, basic or salt groups which are electrovalent in nature and the resin exchanges ions by means of these groups in a manner similar to normal acids, bases or salts. The coordination resins are polymer matrices to which are attached functional groups capable of forming complexes with metal ions and metal salts through covalent linkages whereby more stable molecules are produced.

Coordination resins which contain in their structures substituents which function through the concerted action of salt forming groups and coordinating groups are sometimes considered as a special clas of ion-exchange resins. However, it is well-known that the conventional ion-exchange resins are incapable of recovering heavy metal ions from solution containing a higher concentration of alkaliand alkaline-earth ions because such resins function solely by ion-exchange involving electrovalent bonds, and their performance is determined by mass action laws. This may be illustrated using a cau'on exchange resin as an example. Such a resin contains a croslinked polymer matrix to which are attached functional acidic groups; such polymers may be regarded as insoluble acids. Undoubtedly, the most widely used ion-exchange resin today is the cation resin described in my US. Pat. No. 2,366,007

(1944) and is a sulphonated styrene-divinyl benzene polymer which may be represented by NSO H, wherein R is the polymer matrix and SO H, represents the sulfonic acid groups attached to the benzene rings in the polymer. These polymers will form salts and will exchange its cations with the ion in solution. Thus the sodium form of the ion-exchange resin may be used to soften hard water by exchanging its sodium ions for the calcium and magnesium ions in solution, and because the process is one of ion exchange, leak-through of the calcium or magnesium ions will occur much before all of the sodium in the resin has been exchanged for the calcium or magnesium and the resin will have to be regenerated. The spent resin is regenerated using sodium chloride solutions which direct the equilibrium to reform the sodium salt of the polymer. From the foregoing it is obvious that the cation exchange resin would be incapable of removing small quantities of calcium or magnesium from solutions containing sodium chloride in higher concentrations than the concentration of calcium or magnesium, or that they could remove small quantities of cupric or other heavy metal ions from sodium chloride solution. It has been shown experimentally that in a column, the sodium salt of these resins shows little or no ability to remove copper from a 3 percent sodium chloride solution containing 250 parts per million of cupric ion.

In contrast to this, the coordination resins of this invention containing at least one T group per triazine ring, are able to remove the copper quantitatively from these sodium chloride solutions, and the copper derivative of these coordination resins are not regenerated to the sodium salt by sodium chloride. These results point to the utility of these resins capable of complexing metal cations by coordinations without depending on ion-exchange phenomena, not only in research and in the recovery of metals from processing wastes or from dilute solution, or for the purification of medicinals, food and industrial products or for the control of pollution but also for carrying out such process in the presence of high concentration of alkaline and alkaline-earth salts such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, etc., and for the separation of these heavy metal cations from each other.

These chelating resins, as is the case in ion-exchange resins can be prepared as small discreet particles in granular or bead forms and in these forms are used in columns or containers through which the solution containing the metal ions to be recovered or exchanged is passed. initially, at the beginning of the process the resin efficiency is high and high rates of flow can be used. AF the capacity of the resin is decreased its efiiciency is decreased. Since, in the solid polymer, the rate of the exchange or the coordination reaction is diffusion-controlled, the functional groups in the inside of the mass of the polymer are not utilized efficiently unless the rate of the flow of the solution through the bed of polymer particles is sufficiently low. When the capacity of the polymer is exhausted or leadthrough occurs, the process is interrupted and the resin regenerated.

The coordination resins of this invention can also be prepared in other fonns such as in open pore structures such as are obtained by impregnating open-pore natural sponges or synthetic cellulose sponges or polyurethane foams with the soluble, fusible condensation products and thereafter insolubilizing the condensation products in situ. Or they can be prepared in the form of sheets or membranes by impregnating cellulose pulp or paper, cotton mats, wood pulp, fiber board, sawdust board, cotton in the form of mats, woven fabrics, etc. with the intennediate stage of the condensation resins and thereafier insolubilized in situ. Likewise porous ceramic beads, slabs, tubes, etc., derived from fused alumina, silica, etc., can be impregnated with the soluble, fusible condensation products and cured in situ.

The coordination resins can also be prepared in filamentary form by coating or impregnating fibers such as cotton, regenerated cellulose, polyvinyl alcohol, homoand copolymer fibers, etc., with the condensation resins of this invention and then insolubilizing the product in situ. The filamentary form of these new resins of this invention are particularly useful in treating very dilute solutions of metals. In the treatment of very dilute solution, the costly handling of large volumes of solution to recover small quantities of metal, which, together with the high attrition loss of the granular polymer, makes the process uneconomical, as for example, to recover one part of copper from a solution containing 250 parts of copper per million, it is necessary to process 4,000 pounds of the solution, whereas if the solution contains only 100 parts of copper per million, then l0,000 pounds of solution must be treated. The use of the filamentary form eliminates some of the problems associated with the conventional granular processes by (l) preparing and using insoluble coordination polymers in filamentary form rather than in the form of discrete particles or membranes and (2) contacting the solution with the coordination resin in filamentary form. A further improvement consists in contacting the solution containing the metal cations with a new surface of the filamentary coordination polymer before substantial exhaustion of the capacity of the coordination polymer occurs by advancing the filamentary polymer intermittently or continuously is desired or required. Furthermore, the solution may be treated in a batch process or in a continuous-flow system. Further improvements and modifications of the process of this invention include the continuous regeneration of the filamentary coordination resin as well as a continuous cyclic system which comprises contacting the solution of metal cations with the filamentary coordination polymer, regenerating the coordination polymer and recontacting a solution containing the metal cations with the regenerated coordination polymer.

The filamentary form of the coordination polymers used in the practice of this invention may be prepared and used in various forms depending upon the particular use desired and economic considerations. They may be prepared as single solid continuous-filaments similar to the commercial monofilament fishing lines of various diameters from about 0.005 to 0.05 inch or higher in diameter; or in smaller diameters, which may be braided, twisted or woven into soft, pliable multifilament lines of various diameters. They may also be used in the form of hollow lines to increase the buoyancy of the filament, or in the form of a solid or hollow ribbon. Where long lengths of the filamentary coordination polymers are to be used in the process of this invention, and where there is danger of breakage due to the weight of unsupported polymer exceeding or approaching the limit of the tensile strength of the coordination polymer, the polymer may be reinforced by use of a reinforcing core of another filament such as another fiber, strands of fibers, wire, strands of wire or by forming a mixed, twisted, braided or woven filament with other reinforcing filaments. In other cases, the coordination polymer may be used as a coating on a core of fiber, fibers or wore. The choice of the specific form depends on the methods used in preparing the filamentary coordination polymer from the intermediate available as well as the cost of the particular form prepared and the specific use made of the filamentary coordination polymer.

The behavior of the coordination groups in the compounds and resins of this invention is determined by their stability constants. Thus, when a coordinating group as illustrated by a mole of CHzC O O Na tim 9 Na CHnCOO CHzC O O CID-H2O will form, and with a solution of a mole of nickel chloride, NiCl the structure will form, and in another solution containing one-half mole of CuCl and one-half mole of NiCl one-half mole of each of these chelate structures will be formed. On the other hand, if a coordinating group having a mole of imino diacetic acid coordinating groups is reacted with a solution containing 1 mole of copper chloride and one mole of nickel chloride, only the copper chelate will form because the stability constant of the copper chelate (K, is about 3.5 l0') is greater than that of the nickel chelate (K, is about 275x10 and, for the same reason, if the nickel-chelated polymer is immersed in a solution of copper ion, the nickel will be replaced by copper and nickel will go into solution, even though these metal chelates are not regenerated by alkali ions.

For the iminoacetic acid group the qualitative order of selectivity is Pd* Cu Fe* Ni Pb Mn* Ca Thus, if a mole of each ion is in solution, seven moles of iminoacetic acid groups will be required on the polymer to react with the six heavy metal ions and they will be absorbed simultaneously if sufficient iminoacetic acid groups are in contact with the solution, but if only one mole of iminoacetic acid groups is in contact with the solution, then only the lead is removed, and if two moles of iminoacetic acid are in contact with the solution, then lead and copper are removed, and if three moles of irninoacetic acid groups are in contact with the solution, then lead copper and iron are removed, and similarly for 4, 5, 6, etc., number of metals.

In the triazine derivatives, the activity of a coordination group, such as N( CH COOH etc., depends on the manner the group is attached to the triazine ring. For example, I have discovered that when such groups are attached directly to the triazine ring, as in such compounds as (NI-1 M C N )NHCH COOH, (NH (C N )N(Cl-l ooh. (C N )(NHCl-l,COOl-l) (C N )(NCH COOH) the coordination tendency of the aminoacid nitrogen is greatly reduced and that the substituent group functions more nearly as a carboxylic acid forming primarily electrovalent bonds; while the exact reason for this behavior is not thoroughly known, it may be explained on the basis that the basicity of the amino acid nitrogen has been greatly reduced by the attachment to the carbon atom in the triazine ring. Whether or not his theory explains this-phenomenon satisfactorily, l have now discovered that if the amino nitrogen of the amino acid is attached to the carbon atom of a triazine ring by means of another atom or group of atoms so as to preserve the basicity of the amino nitrogen of the amino acid, then the coordination tendency of the amino acid is maintained. Accordingly therefore, the T groups attached to the triazine ring are substituted amino acids in which at least one amino group is basic. These properties are found in the T groups defined hereinabove having the general formulas,

R1 R2 R1 I I NN ,N-CHR(CHR N defined hereinabove.

The following examples illustrate the practice of this invention and are given by way of illustration and not by limitation. Unless specifically indicated otherwise, the parts and percentages are intended as parts by weight and percentages by weight, respectively.

EXAMPLE I A slurry of cyanuric chloride is prepared by running a thin stream of a hot solution of 184.4 g. of cyanuric chloride in 400 ml. of acetone into 600 ml. of stirred mixture of ice and water (O-5aL C), and 366 parts of Nl-l NHCI-I COONa added and the temperature raised slowly to 45 C, followed by the addition of 166 parts of Na CO and the mixture heated to reflux for 2 hours, cooled, acidified with dilute I-I SO, and cooled to 5 C; the triazine is removed by filtration. The filtrate is evaporated to dryness and extracted with anhydrous ethyl alcohol to recover addition product and there is obtained an almost quantitative yield of (C N )(NHNHCI-I,COOI-I) which, on analysis for C, H and N gives values of 31.21 percent C, 4.4 percent H, and 36.28 percent N, which values are in good agreement with the theoretical values for the compound.

EXAMPLE II The procedure of Example I is repeated using 576 parts of NI-I N(CH COONa) and there is obtained the compound (C N:;)[NHN(CH COOH):]n which on analyses for C, H. and N gives values of 34.61 percent C, 4.04 percent H, and 24.2 percent N which values are in close agreement with the theoretical values for the compound.

EXAMPLE III EXAMPLE IV The procedure of Example 111 is repeated using 144 parts of (NI-I (CB3N )CI prepared by the procedure of J.A.C.S., 73, 2981 (1951), and 192 parts of Nl-I N(CH COONa) and there is obtained the compound (NI-I (C N )NHN(CI-I COOH) EXAMPLE v The procedure of Example IV is repeated using 162 parts of (CH NH) CC3N CI (prepared by the procedure given in J.A.C.S., 73, 2981 (1951). and there is obtained the com- EXAMPLE VI The procedure of Example 1V is repeated using 270 parts of (NI-I )(H NO SC H NH)(C N )Cl, prepared by the method of J. Org. Chem., 24, 643 (1956), and J.A.C.S., 73, 2981 (1951) and there is obtained the compound (NI-I XI-I NO SC I-LN l-I)(C N )NHN(Cl-l COOl-I) EXAMPLE VII The procedure of Example IV is repeated using 203 parts of (NI-I )(NI- I ONI-INH)(C N )C1 (prepared by the method of US. Pat. No. 2,295,562) there is obtained the compound, (Nl-l )(Nl-I ONHNl-l) 3N )Nl-IN(CI-l COOl-l) EXAMPLE VIII The procedure of Example III is repeated using 209 parts of I-IOCl-I-,,CI-I NI-I(C NQCI, prepared by the procedure of J.A.C.S., 73, 2986 (1951), and there is obtained the compound l-lOCl-I CH,Nl-I( C N )[NHN(CH,COOH) EXAMPLE IX The procedure of Example 1V is repeated using 233 pans of (HOCI-I Cl-I H)- C N Cl prepared by the procedure of J.A.C.S., 73, 2986 (1951), and there is obtained the compound (HOCI-I CH NH) C N NHN(Cl-hCOOl-I) EXAMPLE X The procedure of Example III is repeated using 344 parts of (HOCH2CH2)2N(C3N3) (C 2). prepared by the procedure of J.A.C. S., 73 2986 (1951), and there is obtained the compOLlnd EXAMPLE XI The procedure of Example IV is repeated using 285 parts of (NaOOCCH NI-D N CI (prepared by the procedure of J. Org. Chem, 24, 643 (11959)) and there is obtained the compound (HOOCCH NH) (C N )N1-IN( CH COOH EXAMPLE XH The procedure of Example III is repeated using 267 parts of CH,-CHC.,H NH(C N )C1 (prepared by the procedure of J.A.C.S., 73, 2981 (1951)) using Cl-I -CHCJ-LNl-h N )Cl;, and there is obtained the compound Cl-h-CI-IC H4NH(C3B}B)INHN(CH2COOH)2]2- EXAMPLE XII] The procedure of Example IV is repeated using 330 parts of (Cl-I Cl-IC lLNl-DAC NQCl (prepared by the procedure given in .I.A.C.S., 73, 2986 (1951)) and there is obtained the product (CI-l Cl-IC I-l NI-I) (C N )NHN(CH COOH) EXAMPLE XIV The procedure of Example III is repeated using 269 parts of CI-I CHCJ-I O(C N )Cl (prepared from CI-I CI-IC H ONa and (C N )C1 using the procedure of J.A.C.S., 73, 2989 (1951)), and there is obtained the compound CH CHC l-l O(C N )[NI-IN(CH COOl-l) When the procedure of Example IV is repeated using 334 parts of (CH, CHC I-LO) (C N;,)Cl, there is obtained the compound (CH, Cl-IC H O) (C N )NHN(Cl-I COOH)=.

EXAMPLE XV The procedure of Example IV is repeated using 227 parts of (CH CHCI-I O) (C N )Cl (prepared from CH CHCH OI-I and (C N )Cl according to J.A.C.S., 73, 2988 (1951)), and there is obtained the compound (Cl-I CHCH O)2(C N )NI'IN(CH COOH) EXAMPLE XVI The procedure of Example IV is repeated using 31 1 parts of (CH CI-ICH OOCCH O) C N CI (prepared from HOCH COOCH CH CH according to J.A.C.S. 73, 2988 1951)) and there is obtained the compound (CH CHCl-I OOC.CH2)2(C3N 3)NHN(CH2COOH)2.

EXAMPLE XVII The procedure of Example II is repeated at 5 C using 384 g. of NH N( Cl-I- COONa) 184 g. of cyanuric chloride in acetone, and 106 g. of Na CO and there is obtained the compound Cl(C3N.q)[NHN(CH2COONa)2]2.

Then there is added 376 parts of I-I(O CH CH OH and 40 g. of NaOl-I; the mixture refluxed for one hour and there is obtained a solution of the compound l-I( 0CI-l CI-I=) O(C -,N NHNMCCLCOONah.

EXAMPLE XVIII Example XVII is repeated to form the Cl(C N Ifll -lN(CI-l COONa) compound. Then therg isadded ethylene diamine and the mixture refluxed for 2 hours. There is obtained the compound [(NaOOCCl-I NNH] (C N )NHCH CH2NH(C N3)[NHN(CH COONa)2]2.

EXAMPLE XIX Example XVII is repeated to prepare the CI(C N NHN(CH COONa compound, and there is added 4 3 g. of ethylene imine and the mixture heated to 40 C for 30 minutes, while a dilute solution of NaOI-I IS added to maintain neutrality. There is obtained in solution the compound N C3Ni) [NHN (CHzC O N8) 2]: II:

EXAMPLE XX A slurry of 368 g., of cyanuric chloride in 800 ml. of acetone and 1,200 ml. of water are reacted with 440 parts of (NI-I )(SO a)C H CI-I =CHC I-I (SO Na)(NI-I and 106 parts of Na CO at 10-15 C. There is obtained the intermediate in theoretical yield,

S OaNa S OsNa One-half of this compound is reacted with 384 g. of NI-I N(CH,COONa)- according to the procedure of Example III, and there is obtained the compound s OzNa NH c,N=)1NHN c1120 0 OH) 111,

S OzNa which showed marked fluorescent properties. The other half of this compound is first reacted with ammonia by the procedure of J.A.C.S., 73, 2981 (1951) and then with 192 parts of NI-I N(CH COONa)- by the procedure of Example IV, and there is obtained the compound [(HO O G CHahNNH] (NHa) CgNtNH CH 8 OrNa S OzNa which also has marked fluorescent properties.

EXAMPLE XXI A mixture of 141 parts of (NI-I (C N )(NI-INI-I 222 parts of ClCH COONa, and parts of NaOH dissolved in 750 parts of water and refluxed for one hour. There is obtained a solution of the compound (NI-I (C N' )I lI-IN(CI-I COONah.

EXAM PLE XXII can be readily prepared.

Same as above Y Groups Same as above Same as above CaHn CeHu

The triazine compounds of this invention containing at least one T group wherein the COOl-l group is in the acid form, may be used in the acid form or they can be used in the form of salts. The salts are readily obtained by reaction with bases such as NaOH, LiOI-I, Ca(OI-I) Mg(OI-l KOH, etc., or the corresponding oxides where available such as CaO, MgO, etc., or the free acid may be converted to ammonium salts by reaction with ammonia and the substituted ammonias such as the amines, hydrazines, hydroxyl amines, etc., for example, amminia, methyl amine, ethyl amine, dibutyl amine, ethanol amine, diethanol amine, triethanol amine, hydranne, N- methyl hydrazine, dimethyl hydrazine, phenyl hydrazine, ethylene diamine, diethylene triamine, phenylene diamine, pyridine, morpholine, piperazine, allyl amine, diallyl amine, propargyl amine, semicarbazide, guanidine, biguanidine, guanazole, trimethyl benzyl ammonium hydroxide, etc., as well as bases such as triphenyl phosphine, tributyl stilbine, etc. For other purposes the T group can possess the carboxyl structure in the form of an ester which is then hydrolyzed by acids and bases to produce the free acid or a salt, thus N-CHzCOONa CHIOH /NCH2COOO:H5 1110 /NCH:C OOH C HsOH The new coordination compounds of this invention are readily prepared from the free acids of the new triazines of this invention and the corresponding oxides of the metal desired. However, they are more easily prepared by reacting a water soluble or water dispersible salt of the triazine compound with a water soluble metal derivative such as copper sulfate, nickel chloride, etc.

For example, when a solution of C N;,[l-Il-IN(C'H,COOl\la) is treated with a solution of CuSO a blue complex is form ed which precipitates from the solution, whereas when a solution of a cobalt salt is used, a red, insoluble precipitate is obtained. These dried precipitates do not change color substantially on exposure to U.V. light or when heated to 100 C for 24 to 48 hours. Also, when these metal salts are reacted with the compounds of Examples 1 to XVI inclusive, coordination complexes are similarly obtained. Furthermore, when solutions of silver, cadmium, aluminum, chromium, iron, zinc, lead, titanium, uranium, zirconium, vanadium, uranium, palladium, lanthanum, mercury, nickel, and manganese are used instead of copper and cobalt, coordination complexes are also obtained with the compounds of Examples 1 to XX inclusive.

EXAMPLE XXIII (NH C N )NHN HCH COOI-I Aqueous formaldehyde (37.2%)

parts 32 parts reflux, as described above, the mixtures can be shaken or stirred for a longer period, for example, 24 to 72 hours or longer at room temperature, to effect reaction between the components and to obtain a soluble, fusible reaction product which can be heat-hardened. This condensation is performed preferably in the presence of an alkaline condensation catalyst, such as sodium hydroxide, sodium carbonate, ammonia, triethanolamine, hexamethylene tetraamine, etc., and cured in the presence of acidic curing catalyst, or catalysts which under the influence of the reaction or heat produce acidic substances, such as acetic acid, phthalic acid, ammonium phosphate, ammonium chloride, glycine, chloroacetamide, chloroacetyl urea, etc.

EXAMPLE XXIV (NH- ),(C N=,)NHNHCH,COOH 40 parts Aqueous formaldehyde (37.2% CH- .0) 32 parts are heated together under reflux at the boiling point of the mixture, yielding a condensation product, a sample of which cures to an insoluble, infusible state when a sample is heated at l30-l50 C on a hot plate. The remainder of the solution is neutralized with 10 percent HaOl-l to give the sodium salt of the condensation product, a sample of which also cures on a hot plate to an insoluble, infusible state at l30-l50 C. To the remainder of the solution is added 16 parts of CuSO,,in a 10 percent aqueous solution, and there is obtained the copper coordination compound of the resin having the linkages color. A sample of the copper derivative of the resin is also converted to the insoluble, infusible state by heating at -l 50 C.

Coordination compounds are also formed when cobalt, nickel, iron, zinc, and cadmium ions are added to the sodium salt of the condensation product.

EXAMPLE XXV (CH,NH),(C,N,)NHN(CH,COONa), 62.6 parts Aqueous CH,O (37.5%) 24.0 parts NaOH in 10 parts ",0 0.2 part The above ingredients are refluxed for fifteen minutes to produce a resin dispersion which, when dehydrated, produces a clear, viscous resin and which, on heating to C. becomes hard and infusible. In many cases, it is desirable to condense this and other triazines with melamine and formaldehyde, or with urea and formaldehyde, phenol and aldehydes, etc., as shown in some of the subsequent examples.

When an equivalent amount of glyoxal is used in this example, faster curing of the resin is obtained.

The above ingredients are refluxed for 25 minutes to produce a clear syrup. On dehydration it cures slowly at 140 C, but on the addition of 5 parts NI-I Cl, the cure is accelerated. The addition of 80 parts of alpha flock to the syrup produces a molding compound, which, after being dried at 70 C has an excellent cure and good flow when molded at l35 C for 4 minutes. The product has a glossy surface and is light-colored. When an equivalent amount of thiourea is substituted in the above formula, the type of cure, molding characteristics, and appearance of the molded product obtained is substantially the same as with that of urea.

EXAMPLE XXVII (NH;)2(C N:,)NI-IN(CI-I COONa) 142 pans Paratoluene sulfonamide 57 parts Aqueous CH;O (37.5% CH O) I90 pans The above ingredients are refluxed for 1 hour to produce a syrup which is clear while hot and cloudy on cooling.

EXAMPLE XXVIII (NH2)2(C3N3)NHN(CH2COOLI)2 142 parts Aqueous C (37.5% CH O) 190 parts Phenol 29 parts The above ingredients are refluxed for 25 to 30 minutes to give a clear syrup when hot. At 135 C the syrup has a prolonged cure but when 7.5. parts of chloroacetamide are added to the composition, an excellent cure is obtained.

EXAMPLE XXIX (NH,) (C;,N )NHN(CH COOK) 95 pans Melamine 63 parts Aqueous CHgO (37.5% C11 0) 220 pans The above mixture is refluxed for fifteen minutes. The syrup is clear when hot, when dehydrated cures alone at l35l40 C.

EXAMPLE XXX The above components are mixed and refluxed for 15 minutes. The syrup does not cure well alone at I35 C, but the addition of 8 pans of chloroacetamide accelerates the cure.

EXAMPLE XXX] (H N )(I-I NO SC I-LNI-I)(C N )NHN(CH COONa) 130 parts Aqueous CPI- O (37.5% CH O) 2 l0 pans NH in parts H 0 2 parts Aqueous trimethylol melamine (50% solu.) 130 parts When the above ingredients are refluxed for 20 to 30 minutes a syrup is obtained which cures slowly alone. The cure is accelerated by ammonium chloride to produce hard resins and molding compounds.

EXAMPLE XXXII (NH2)(NH CONHNI-I)(C N )NHN(CH z H )2 I30 pans Aqueous CH O (37.5% CH O) I30 parts Glycerine parts The above mixture is refluxed for 25 to 30 minutes to produce a clear resin curing at 135-140 C, which cure is accelerated by the addition of curing agents.

EXAMPLE XXXIII (NH,) (C N )NHN(CI'I COOI-I) I25 pans Aqueous CH O (37.5% CH O) 150 parts Butyl alcohol parts EXAMPLE XXXIV (NI-I,) C:,N;,NI*IN(CI-I COOH) I20 pans Aqueous CH O (37.5% C11 0) I50 pans Diethyl malonate 20 parts NaOH in 20 parts H O 2.5 pans are refluxed for 20 minutes to produce a condensation product which cures at 140-160 C.

EXAMPLE XXXV (NH,) (C:,N;,)NI-IFKCH COONa) I20 parts Aqueous CI-I,O (37.5% CH O) 140 pans NH in 5 pans H O 4.0 parts Acetamide 15.0 parts The above mixture is refluxed for 15 minutes to produce a clear syrup which cures alone at C. With phthalic anhydride, chloroacetamide and ammonium chloride, respectively, the cure is accelerated.

EXAMPLE XXXVI :)z( sNa) 2 )2 65 pans Acrolein 38 pans NaOH in 5 parts H O 0.2 pan The reactants are mixed and refluxed for 15 minutes to produce a syrup which cures at C to a hard tough resin by the addition of ammonium chloride.

EXAMPLE XXXVI] Shellac l5 pans The dimethylol derivatives are prepared in accordance with the low temperature procedure of Example XXIII. The above components are mixed well and fused at l50 C. At this temperature, the mixture cures to a hard, infusible resin. The addition of paraform and hexamethylene tetraamine, respectively, hastens the cure.

EXAMPLE XXXVIII Alkyd resin (cg. glyceryl phthalate) 50 pans HOOCCH,NHNH-(C N )(NHCH,OH l5 pans These components are mixed together and heated on a hot plate at C, and cures to a hard, infusible product. The curing is accelerated by paraform.

EXAMPLE XXXIX l-Phenyl guanazole 35 parts Aqueous formaldehyde (37.5% CH O) 35 parts Ammonia (28%) 2 parts Aqueous NaOH (0.5 N) 0.75 pan Reaction product of Example XXIII 9 parts are heated together under reflux for 5 minutes at the end of which period separation of a resinous mass occurs. This resin is used satisfactorily for the production of molding compounds.

EXAMPLE XL Soya bean protein 25 parts Aqueous ammonia (28% NR 2.5 parts Aqueous NaOH (0.5 N) 3.0 parts Aqueous CH O (37.5% CH,O) I50 parts (NH (C,,N )NHN(CH COONH )2 80 parts are heated together under reflux at the boiling point of the mixture for 20 minutes. The resin cures well when dehydrated and heated at 130 C.

EXAMPLE XLl 100 parts IOOparts are mixed together and then heated for forty hours at 60 C. The resinous material thereby obtained melts on a hot plate at 140 C, and is converted to an insoluble, infusible state by further heating.

EXAMPLE XLII The procedure of Example XXIV is repeated using 51.4 parts of and 64 parts of aqueous 37.5 percent CH O, and the resin dehydrated and tested. The dissociation constants, using the method given in .l.A.C.S. 74, S052 (1952) as determined qualitatively are about k, -4.5 l' and k 6.6 l0"'". Separate samples of the condensation product are neutralized with NaOH, KOl-l, LiOl-l, CaOl-l, Ca(Cl-l) Ba(OH) and Sr(OH) respectively, to give the corresponding salts of polymer products.

EXAMPLE XLIll The procedure of Example XXIV is repeated using 51.4 parts of (NI-I (C N )NHN(CH COOH) and 64 parts of aqueous 37.5 percent C11 0 and separate samples of the condensation product is neutralized with ammonia, hydrazine, N- methyl hydrazine, dimethyl hydrazine, methyl amine, ethyl amine, butyl amine, diisopropyl amine, tributyl amine, ethylene diamine, diethylene triarnine, ethanol amine, diethanol amine, triethanol amine, aniline, phenylene diamine, arninophenol, dimethyl amine, pyridine, morpholine, polyethylene irnine (MW 300), piperidine, hexamethylene diamine, tetramethylene diamine, allyl amine, and propargyl amine and the corresponding salts are obtained.

EXAMPLE XLIV The procedure of Example XL is repeated and the product of the condensation is poured into a glass tray and placed in an oven heated to 100 C for 12 hours, followed by heating at 130 C for 6 hours. The product is crushed into granules of about 50 mesh and immersed in a SOO-part of a percent solution of NaOl-l to form the sodium salt. The granules are then washed with distilled water to remove mechanically held NaOH and kept in a moist condition.

Twenty-five parts of the Na salt of the resin are added to 100 parts of solution containing 5 parts of CuCl, and allowed to stand for 1 hour. The resin becomes blue in color and the copper becomes substantially exhausted from the solution. Similar exhaustions are obtained when a 1 percent solution of CuCl in a 3 percent NaCl solution, or a 0.1 percent solution of CuClin a 1 percent NaCl solution is used.

Recovery of copper is also obtained from solutions containing other alkali and alkali-earth salts such as the salts of potassium, lithium, magnesium, calcium, strontium, such as their chlorides, nitrates, sulfates, phosphates, and acetates. For example, all of the copper is recovered readily from a 15 percent calcium chloride solution having 25 ppm of copper ion, as well as when the potassium, lithium, cesium, barium and calcium salts of the coordination resin is used. Using the procedure described by J. Bjerrum (Metal Amine Formation in Aq ueous Solution," publisher Haase and Son, Copenhagen, 1941) it is determined that the polymer forms both l:l and 1:2 chelates whose stability constants are approximately K 5.75 X 10*, and K 1 .52X 10. The polymer also forms coordinate compounds with ferric chloride corresponding to a 1:1, 1:2 and 1:3 below pH values of about 8.5, and the stability constants of these compounds are approximately about K 1 .25 l0, K -4.55 l0 and K, 8.1Xl0.

EXAMPLE XLV The procedure of Example XLlV is repeated with cobaltic chloride solutions and the metal is recovered in a similar manner. During the process the coordination polymer becomes red as it reacts with the cobalt ions.

When solutions of silver, cadmium, molybdenum, aluminum, cesium, lanthanum, chromium, manganous, manganic, ferrous, ferric, nickel, zinc, lead, platinum, palladium, vanadium, tantalum, zirconium, titanium, and uranium ions are used instead of the cobalt ions, they are also recovered in a similar fashion.

EXAMPLE XLVI Using the procedure of example XLlV, coordination derivatives are formed with the individual resins of Examples XXVI! to XLI inclusive, with copper an the metal ions of Example XLV.

The aldehyde-amidogen polymers represent only one type of condensation polymers that can be prepared from the new reactive triazine compounds of this invention through condensation polymerization reactions. By condensation polymerization is meant an intermolecular reaction involving at least one of the triazines of this invention with at least one related polyfunctional molecule, which as a result of inter-reaction liberates a by-product molecule. Condensation polymers, other than the aldehyde-amidogen polymers such as the polyester-, the polyamide-, the polyalkylene-, the polyaryleneetc., types are also readily prepared from the reactive triazine compounds of this invention; and, all of these polymers have, as a repeating unit, the same fundamental moiety, namely, a 1,3,5-trian'ne to which is attached at least one T group and these polymers have the property of coordinating with metal ions, which pro perty is conferred to the polymer from the triazine compound from which they are prepared.

Another modification of condensation polymerization is the reaction of a preformed polymer containing active hydrogens with the triazine compounds of this invention, which contain functional or reactive groups. Illustrative of such polymers are cellulose and cellulose derivatives, polyvinyl alcohol and its copolymers, polyacrylic and polymethacrylic acid and its copolymers, polyacrylamide and its copolymers, phenol-formaldehyde resins, polyethylene imines, etc.

These same characteristics, namely, (1) the property of coordinating with metal ions and (2) the existence, in the re peating unit, of the triazinyl moiety to which is attached at least one T group, are also found in the addition polymers prepared from the reactive intermediates of this invention.

By an addition polymerization is meant an intermolecular reaction involving at least a triazine of this invention which occurs without the formation of by-product molecules. The preparation of addition polymers from the new triazine compounds of this invention is readily demonstrated by the polymerization of the new triazine derivatives which have at least one polymerization ethylenic group attached to the triazine ring, such as illustrated by CH =CHC H NH(C;;N; T2, CHC$H4NH)2C;1N:\(T), NH(C3N3)T3, Cic- These compounds are vinyl types monomers from which polymers may be prepared by methods well known in the polymer art. They may be polymerized alone or with each other or with other monomers to produce fusible or crosslinked polymers and copolymers suitable for chelating resin use as well as for pigment production. When the triazine monomer possess only one Cl-i CH- group such as in CH CHC,,H,NH(C N y! and CH CHCOOCH CH NI-KC N )T, then thermoplastic polymers are obtained, whereas when the triazine monomer contains at least two CH CH groups then crosslinked polymers are obtained.

By copolymerizing a monovinyl triazine compound of this invention with a divinyl triazine compound, crosslinked copolymers are obtained. Such crosslinking can also be obtained by using a monovinyl triazine compound with another crosslinking can also be obtained by using a monovinyl triazine compound with another crosslinking agent which is not a triazine. Such crosslinking compounds can possess a multiplicity of vinyl vinylene or vinylidene group.

A few illustrative examples of crosslinking monomers, that is, monomers having a multiplicity of vinyl, vinylene or vinylidene groups are divinylbenzene, divinylnaphthalene, vinyl isopropenyl benzene, vinyl allyl benzene, diisopropenyl benzene, diallyl benzene; the polyunsaturated esters such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, diallyl itaconate, glycol rnaleate, diallyl succinate, divinyl phthalate, diallyl maleate; the polyunsaturated ethers such as divinyl ether, trimethylene glycol divinyl ether, hydroquinone divinyl ether, catechol divinyl ether, resorcinol divinyl ether, hydroquinone diallylether, catechol diallyl ether, resorcinol diallyl ether; vinyl allylphenyl ether, vinyl vinylphenyl ether, allyl vinylphenyl ether, vinyloxy-vinyl benzoate, vinyloxy-allyl benzoate, allyloxy allylbenzoate; the polyunsaturated amides such as ethylene diacrylamide, ethylene dimethacrylamide, N-vinylacrylamide, N,N'-divinylphthalic diamide, N,N'-diallylphthalamide, etc., and other polyunsaturated modifiers such as vinyl phenylacrylate, 2-isopropenyl-5-acryloxynaphthalene, vinyl-3,5-diallyloxypalmitate, etc. The crosslinking monomers may be used alone or in conjunction with each other or with other monomers having one vinyl, vinylene or vinylidene group such as vinyl chloride, vinylacetate, vinylpropionate, vinylbutyrate, vinylstearate, acrylonitrile, rnethacrylonitrile, vinylidene chloride, vinylene cyanide, -chloroacrylonitrile, acrylic acid, the acrylic esters such as the methyl, ethyl, propyl, butyl, etc. acrylates; methacrylic acid and its esters such as the methyl, ethyl, propyl, butyl, hexyl, phenyl, etc. methacrylates; itaconic anhydride, itaconic acid and their monoand diesters, such as the methyl, ethyl, propyl, etc. esters; the acrylic, methacrylic, chloroacrylic and the cyanoacrylic amides, N-alkyl amides, N,N-dialkyl amides; the alkenylaryl compounds such as styrene, the monomethyl styrenes, the dimethyl styrenes, alphamethyl styrenes, the mono-, diand trichlorostyrene, the rnand p-acetarnido styrenes; vinyl naphthalene, vinyl carbazole, etc.; the alkenylaryl heterocyclic compounds such as vinyl pyridine, vinyl methyl pyridine, vinyl quinoline; the diene-1,3 compounds such as butadiene-l,3, isoprene 2,3- dimethyl butadiene-1,3,chloroprene, 2-phenylbutadienel ,3, methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, N-vinyl imidazole, the vinyl azlactones, the N-vinyl-2- oxazolidinones, maleic anhydride, dimethyl rnaleate, etc.

These polymers and copolymers may be prepared in mass, in solution, in suspension and emulsion systems, using the accepted initiating systems, such as the per compounds which generate radicals, or thermally, or with ultraviolet light or with ionizing radiation and in some cases with ionic catalysts, both anionic and cationic, e.g., RF NaNl-l, BuLi, HF, etc.

The formation of other types of addition polymers from the triazines of this invention is illustrated further by the reaction through ring opening of triazine compounds containing at least one T group and another group containing the structure EXAMPLE XLVlI Example XVll is repeated to obtain the compound Cl(C N )[NHN(CH COONa)1] then there is added 440 g. of polyvinyl alcohol (mol. wt. of about 4,000) in 8,000 parts of water and 40 g. of NaOH and the mixture heated to C. with stirring for about 3 hours. There is obtained a viscous aqueous dispersion of a polymer having one in 10 hydroxyls converted to a cyanurate of the triazine compound of the general formula which fonns coordination compounds with copper ions and with the metal ions of Example XLV.

EXAMPLE XLVIII Example XVII is repeated to prepare the compound Cl V(CSN3[NHNQCH2ACOVONE)2J, then there is added for each mole of this compound 825 parts of soda-cellulose (i.e. one mole of NaOH for each anhydroglucoside unit) in 8,000 parts of water and the mixture heated at 75-85 C. for 4 hours, following which it is acidified with dilute hydrochloric acid and there is obtained the triazinyl cellulose derivative having about 1 to 5 glucoside units as a cyanurate of the general formula CHOH-CHOH C CHO which forms coordination compounds similar to the polymer derivative of Example XLVII.

EXAMPLE XLlX To 39.7 parts of (HOCH Cl-I Nl-I),,C N NHN(CH COONa) in 400 parts of water in a reaction vessel equipped with a stirrer and heating means, is added slowly with stirring at 4550 C. a solution of 20.1 parts adipoyl chloride, ClOC(CH COCl in 100 parts of carbon tetrachloride and there is obtained the polymer, after removal of water and CCl corresponding to the structure r & -OCHzCHzHN-$ N l NHNlCHzCOOH]: n

which exhibits coordination properties.

EXAMPLE L The procedure of Example XLlX is repeated using 33.1 parts of NH NH) C N NHN(CH COONa) with 20.l parts of adipoyl chloride and there is obtained the polymer with the repeatin g structure,

which exhibits coordination properties.

EXAMPLE LI Forty-five and five-tenths parts of (C H O) C N NHN(CH COONa) and 6.0 parts of H NCH CH NH are refluxed in 200 parts of dioxane for 8 hours, and then 20 parts of 36 percent aqueous HCl added and the water and dioxane removed at 1.5 mm pressure and the product washed with water to remove sodium chloride and there is obtained a polymer having the structure C-NHCHzCHrNH L I J s NHN(CH1CO OHM EXAMPLE 1.11

The procedure of Example Ll is repeated using 10.8 parts of p-phenylene diamine instead of ethylene diamine and there is obtained a polymer having the structure l IHN(CH CO OH):

EXAMPLE Llli To 34.] parts of in 500 parts of tetrahydrofuran is added one part of tributyl amine and the mixture refluxed for 1 hour and then the furane removed at reduced pressure, leaving a polymer having the repeating unit,

oomo 11 L .In

EXAMPLE LlV Fifty parts of distilled water, 0.5 parts of hydroxy apatite (0.005 to 0.2 micron size), 0.! part of sodium dodecyl- 70 benzenesulfonate, 0.1 part of benzoyl peroxide and 30 parts of CH Cl-lC l-l Nl (C N )Nl-lN(CH COOC H 2 are mixed in a suitable reaction vessel under deoxygenated nitrogen and stirred for 28 hours at 90-95 C. and the polymer is isolated by filtration, washed with alcohol and refluxed for 12 hours,

with 500 parts of percent alcoholic KOH, then neutralized with aqueous HCl to produce the polymer having the structure 5 ECHz-CH}:

CQHIIITH 15 The procedure of Example LIV is repeated using 30 parts of (CHFCHCOOCH2CH2N H)-. .(".-4N;,N H(H- -('H ,N(("H COOH and there is obtained the cross-linked polymer having the repeating unit NHCH2CHgN(CH2COOH)z l \R crnnccoocmcnmno lwricrnc13200001141112 L s .1

EXAMPLELVI Forty-nine parts of HOCl-l,CH N(C N )[Nl-ICH CH,N(CH ooh. are heated in a reaction flask in nitrogen at 160 C for 4 hours or until about 2 parts of water are eliminated, The reaction is then cooled and a crosslinked polyester resin having coordination properties obtained having the repeating structure NHCHzCHzN(CH2COOH)2 N% \N -OH2CCHzHN--( 3 g-NHCHgCH1NCH CO L C HQCOOH which exhibits coordination properties.

EXAMPLE LV" 4 To a mixture of 3 parts of water, 2 parts of triethyl amine, 1

part of glycerine and 30 parts of (H0CH CH NH) C N NH N(CH COONa), is added rapidly with vigorous stirring eighteen parts of toluene diisocyanata and in a short time, foaming occurs and a crosslinked polyurethane having metal coordination properties is obtained.

While the invention has been described in relation to various specific embodiments thereof, it is understood that many substitutions and other modifications thereof can be made within the scope and spirit of the invention.

wherein each of the symbols R, R and R individually represents a radical selected from the class of H, CHRCOOM, phenyl, cycloheptyl, cyclohexyl and an alkyl radical containing one to six carbon atoms and wherein at least one of the radicals represented by R, R and R is CHRCOOM, M is a member consisting of hydrogen, quaternary ammonium group and metals and R represents a member consisting of hydrogen, phenyl, cycloheptyl, cyclohexyl and an alkyl radical containing one to six carbon atoms, n represents an integer of l to 6, and Z represents a divalent aromatic hydrocarbon radical containing six to 12 carbon atoms, the valency of the symmetrical triazine structure which is not occupied by said T groups being occupied by a group selected from the class consisting of hydrogen, hydrocarbon, hydroxy, alkoxyl, carbocyclic aryloxy, hydroxyalkoxy, pyridyloxy, phenylthio, monoalkylamino of one to 12 carbon atoms, -NH phenylamino, CH CHC l-LNH, CH C(CH )C l-I NH-, piperidyl, pyridy], hydrazino, ethyleneimino, NHCl-l Cl-l Ol-l, NHC H OH, Nl-lC l-l As(OH) NHCl-l COOCl-l specified otherwise having no more than 10 carbon atoms and said hydrocarbon groups having no unsaturation therein except aromatic and monoethylenic unsaturation.

2. A triazine of claim 1 which has attached to a carbon atom on the triazine nucleus one group selected from the class consisting of NH a monoalkylamino group of one to 12 carbon atoms, -NHCH;CH,OH, NHC H.,OH, NHC H As(OH),, NHCH,COOCH NHCH CONH (CH CH,O),, H, NHC,H N, -NHCH,CN,

t t i i t UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent: No. 3 i 669 T 963 Dated e 13 1972 Gaetano F. D'Alelio Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 33, line 27, and column 34, line 18, before "specified insert groups eacli of said groups unless N Signed and sealed this 27th day of February 1973.

(SEAL) Attest:

EDWARD M.PLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents DRM PO-1050 (IO-69) USCOMM-DC 60376-P69 i u.si GOVERNMENT PRINTING OFFICE: I959 OS86-334, 

2. A triazine of claim 1 which has attached to a cArbon atom on the triazine nucleus one group selected from the class consisting of NH2, a monoalkylamino group of one to 12 carbon atoms, -NHCH2CH2OH, -NHC6H4OH, -NHC6H4As(OH)2, -NHCH2COOCH3, -NHCH2CONH2(CH2CH2O)8H, -NHC5H5N, -NHCH2CN,
 3. A triazine of claim 1 in which the T group is -NHN(CH2COOM)2.
 4. A triazine of claim 1 in which the T group is -NHCH2CH2N(CH2COOM)2.
 5. A triazine of claim 3 in which the third carbon atom of the triazine nucleus is attached to -NH2.
 6. A triazine of claim 4 in which the third carbon atom of the triazine nucleus is attached to -NH2.
 7. A triazine of claim 3 in which the third carbon atom of the triazine nucleus is attached to -NHCH3. 